Herbicidal 1-cyclopropyl tetrazolinones

ABSTRACT

Herbicidal 1-cyclopropyl tetrazolinones of the formula ##STR1## wherein X represents C 1-3  alkyl, C 2-4  alkenyl or halogen, 
     n represents 0 to 5, 
     R 1  and R 2  each independently represents C 1-6  alkyl, C 2-6  alkenyl, C 2-6  alkynyl, C 3-7  cycloalkyl which may optionally be substituted by C 1-3  alkyl, epoxy-C 3-5  alkan-1-yl, phenyl which may optionally be substituted, or aralkyl which may optionally be substituted, or 
     R 1  and R 2  together with the N-atom to which they are attached, represent a cyclic ring which may be substituted, and some novel intermediates therefor.

The present invention relates to novel 1-cyclopropyl-tetrazolinones, toa process for their preparation, to their use as herbicides, as well asto novel intermediates for their preparation and to processes for thepreparation of such intermediates.

It is known that certain substituted tetrazolinones have herbicidalactivities (see: U.S. Pat. Nos. 4,618,365 (=EP-A-146,279); 4,826,529;4,830,661; 4,956,469; 5,003,075; 5,019,152; 5,120,346; 5,342,954;5,344,814; 5,347,009; 5,347,010 and 5,362,704.

However, the tetrazolinones of the prior art have not been fullysatisfactory, especially in respect of their herbicidal efficacy and/ortheir phytotoxicity against crops.

There have now been found novel 1-cyclopropyl-tetrazolinones representedby the following formula (I), ##STR2## wherein X represents C₁₋₃ alkyl,C₂₋₄ alkenyl or halogen,

n represents 0 to 5, and

R¹ and R² each independently represents C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆alkynyl, C₃₋₇ cycloalkyl which may optionally be substituted by C₁₋₃alkyl, epoxy-C₃₋₅ alkan-1-yl, phenyl which may optionally besubstituted, or aralkyl which may optionally be substituted, or

R¹ and R² together with the N-atom to which they are attached representa ring which may be substituted.

The compounds of formula (I) according to the present invention cab beproduced, for example, by the reaction of a compound of the formula##STR3## wherein X and n are as defined above, with a compoundrepresented by the formula ##STR4## wherein R¹ and R² are as definedabove and

M represents a leaving group such as chlorine, bromine and the like(production method a)).

The compounds of formula (I) according to the present invention havestrong herbicidal activity and exhibit herbicidal function and effectwhich is superior to that of, in particular, the known compoundsdescribed in the above-cited EP-A-146,279 which are somewhat similar tothe compounds of instant formula (I) as well as very good tolerance bycrops.

In this specification, "halogen" comprises fluorine, chlorine, bromineand iodine, preferably fluorine, chlorine or bromine.

Also, "alkyl", "alkenyl", "alkynyl", "cycloalkyl" and "alkan-1-yl" arerespectively a saturated, unsaturated or cyclic ring aliphatichydrocarbon group having the prescribed number of carbon atoms which mayoptionally have a branched chain.

"Aralkyl" comprises benzyl, 1-phenylethyl and 2-phenylethyl preferablybenzyl.

Optional substituents on phenyl and aralkyl include preferably one ortwo of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, C₁₋₄ alkylthio, C₁₋₄ haloalkylthio, cyano, nitro, C₁₋₄alkylcarbonyl, C₁₋₄ alkoxycarbonyl, and/or alkoxyimino-C₁₋₂ -alkyl, orthe like.

The "cyclic ring formed together with the N-atom which may optionally besubstituted" is a 5- or 6-membered monocyclic ring containing at leastone, preferably only one, N-atom, or a benzo-condensed polycyclic ringsuch as pyrrolidin-1-yl, indol-1-yl, indolin-1-yl,1,2-dihydroquinolin-1-yl, 1,2,3,4-tetrahydroquinolin-1-yl, and the like.These rings may optionally be substituted by alkyl such as methyl, ethyland the like, preference methyl.

Advantageously in compounds of formula (I)

X represents methyl, ethyl, vinyl, allyl, 1-propenyl, fluorine,chlorine, or bromine,

n represents 0 to 4, and

R¹ and R² each independently represents C₁₋₄ alkyl, C₃₋₅ alkenyl, C₃₋₅alkynyl, C₃₋₆ cycloalkyl which may optionally be substituted by methyl,2,3-epoxypropan-1-yl, phenyl which may optionally be substituted orbenzyl which may optionally be substituted, the optional substituents onsaid phenyl or said benzyl being independently selected from the groupconsisting of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₂ haloalkyl, C₁₋₂haloalkoxy, C₁₋₄ alkylthio, C₁₋₂ haloalkylthio, cyano, nitro, C₁₋₂alkyl-carbonyl and C₁₋₂ alkoxy-imino-C₁₋₂ alkyl, or

R¹ and R² together with the N-atom to which they are attached representpyrrolidin-1-yl, indol-1-yl, indolin-1-yl, 1,2-dihydroquinolin-1-yl or1,2,3, 4-tetrahydroquinolin-1-yl which may optionally be substituted bymethyl.

Preferably in compounds of formula (I)

X represents methyl, ethyl, fluorine or chlorine,

n represents 0 to 4, and

R¹ and R² each independently represents C₁₋₃ alkyl, C₃₋₄ alkenyl, C₃₋₅alkynyl, cyclopropyl, cyclopentyl, cyclohexyl which may optionally besubstituted by methyl, 2,3-epoxypropan-1-yl, phenyl which may optionallybe substituted or benzyl which may optionally be substituted, theoptional substituents on said phenyl or said benzyl being independentlyselected from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl,difluoromethoxy, trifluoromethoxy, methylthio, ethylthio,trifluoromethylthio, cyano, nitro, acetyl, propionyl and1-methoxyiminoethyl, or

R¹ and R² together with the N-atom to which they are attached representpyrrolidine-1-yl, indol-1-yl, indolin-1-yl, 1,2-dihydroquinolin-1-yl or1,2,3,4-tetrahydroquinolin-1-yl which may optionally be substituted bymethyl.

A process for producing the above-mentioned compounds of formula (I) isillustrated by, the following reaction scheme when1-cyclopropyl-5(4H)-tetrazolinone and diethyl carbamoyl chloride areused as the starting materials: ##STR5##

The compounds of formula (II) include new compounds of the formula(II'): ##STR6## wherein X is as defined above, and

n' represents 1 to 5.

The compounds of formula (II), embracing formula (II'), can be producedby, for instance, a process in which:

b) a compound represented by the formula ##STR7## wherein X and n are asdefined above, is reacted with trimethyl silyl azide in the presence ofa catalytic amount of boron trifluoride ethyl etherate,

c) a compound of above formula (IV) is reacted with sodium azide in apolar solvent in the presence of a catalytic amount of aluminumchloride,

d) a compound represented by the formula ##STR8## wherein X and n are asdefined above, is reacted with trimethyl silyl azide, or

e) a compound represented by the formula ##STR9## wherein X and n are asdefined above, is reacted with a compound of the formula ##STR10##wherein R³ represents hydrogen or methyl.

In the above processes b) and c), the compounds of formula (IV) used asstarting materials include known isocyantes and can be produced, forexample, by the method described in Chem. Ber., Vol. 106, pp. 3753-3764(1973), that is, the reaction of diphenyl dichlorosilane with sodiumazide to obtain diphenyl diazido silane which is then reacted withcyclopropane-carbonyl chloride of above formula (V), or by the methoddescribed in Chem. Ber., Vol. 106, pp. 3765-3768 (1973), that is, by wayof cyclopropane carbonyl azide which is prepared by the reaction of acorresponding cyclopropane carboxylic acid ester with trimethyl silylazide.

The compounds of formula (V) used as starting materials in above processd) comprise acid chlorides and can be easily obtained, for example, bythe method described in Japanese Patent Application Laid-OpenPublication Kokai Hei 2-88535, that is, by reacting cyclopropanecarboxylic acids represented by the formula ##STR11## wherein X and nare as defined above, with thionyl chloride as a halogenating agent.

Further, the compounds of above formula (VIII) can be easily obtainedfor example by reacting vinyl cyclopropanes represented by the formula##STR12## wherein X and n are as defined above, with potassiumpermanganate as the oxidizing agent.

The vinyl cyclopropanes of above formula (IX) are obtained, for example,by the methods described in Liebigs Ann. Chem., Vol. 710, pp. 17-35(1967) and Chem. Ber., Vol. 109, pp.2351-2369(1976).

Also, the compounds of formula (VIII) are easily obtained by hydrolysisof the corresponding cyclopropane carboxylic acid esters. Suchcyclopropane carboxylic acid esters can be produced by any known methodsuch as, e.g., reaction of a diazoacetic acid ester with an olefindescribed in Comprehensive Organic Synthesis (1991), Vol. 4, p. 1031(Pergamon Press); reaction by thermolysis or photolysis of, e.g.,1-pyrazoline carboxylic acid ester described in the same article, pp.953-960; an additional reaction of an α,β-unsaturated ester with carbenedescribed in Shin-Jikken Kagaku Koza (New Lecture Course of ExperimentalChemistry), Vol. 14, p. 86 (Maruzen); a cyclizing reaction of aY-haloester by way of a carbanion described in Shin-Jikken Kagaku Koza(New Lecture Course of Experimental Chemistry), Vol. 14, p. 93(Maruzen); a reaction of an α,β-unsaturated ester with a sulphur ylidedescribed in Advance Organic Chemistry, 3d Edition, p. 773(Wiley-Interscience).

Furthermore, the compounds of formula (VIII) can also be obtained by,decarboxylation of the corresponding cyclopropane: dicarboxylic acids asdescribed in Beilstein, EII9, p. 3.

The compounds of formula (VI) used as starting material in the abovemethod e) can be produced, for example, by the following methoddescribed in Berichte, Vol. 28, pp.74-76 (1895), that is, reaction of acompound represented by the formula ##STR13## wherein X and n are asdefined above, with sodium azide.

Dithiocarbamic acid esters of above formula (X) can easily be obtained,for example, by the reaction of methanenthiol with a compoundrepresented by the formula ##STR14## wherein X and n are as definedabove, or reaction of a compound represented by the formula ##STR15##wherein X and n are as defined above, with carbon disulphide followed byfurther reaction with a methylating agent, e.g., dimethyl sulphate oriodomethane.

The compounds of above formula (XI) can be obtained for example, by themethod, described in J. Hererocycl. Chem., (1990), Vol. 27 (5), pp.1191-1195.

Also, the compounds of formula (XII) can be obtained by the Hoffmanreaction of a corresponding cyclopropane carboxylic acid amide describedin Organic Reactions, Vol. 3, p. 287 or the decomposing reaction of acorresponding cyclopropane carbonyl azide, e.g., Curtius rearrangement,described in the same article p. 337.

The compounds of formula (VII) used in the production method e) as thestarting materials are known per se and are specifically exemplified byethyleneoxide or 1,2-epoxypropane.

Typical examples of compounds of above formula (II) are:

1-cyclopropyl-5(4H)-tetrazolinone,

1-(2-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(1-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dimethylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,3-dimethylcyclopropyl)-5(4H)-tetrazolinone,

1-(1,2,2-trimethylcyclopropyl)-5(4H)-tetrazolinone,

1-(1,2,3-trimethylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2,3,3-tetramethylcyclopropyl)-5(4H)-tetrazolinone,

1-(1- ethylcyclopropyl)-5(4H)-tetrazolinone,

1-(2-ethylcyclopropyl)-5(4H)-tetrazolinone,

1-(1-ethyl-2-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2-ethyl-3-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2-n-propylcyclopropyl)-5(4H)-tetrazolinone,

1-(2-isopropylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dimethyl-3-vinylcyclopropyl)-5(4H)-tetrazolinone,

1-[2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropyl]-5(4H)-tetrazolinone,

1-(2,2-dichlorocyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dibromocyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-difluorocyclopropyl)-5(4H)-tetrazolinone,

1-(2-chloro-2-fluorocyclopropyl)-5(4H)-tetrazolinone,

1-(2-chloro-2-fluoro-1-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dibromo-1-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dibromo-1,3-dimethylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dichloro-1-methylcyclopropyl)-5(4H)-tetrazolinone

1-(2,2-dichloro-1,3-dimethylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-difluoro-1-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dichloro-3-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dichloro-1,3,3-trimethylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dichloro-1-ethylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dichloro-1-ethyl-3-methylcyclopropyl)-5(4H)-tetrazolinone,

1-(2,2-dichloro-1-isopropylcyclopropyl)-5(4H)-tetrazolinone, etc.

Compounds of formula (III) which are reared with the compounds of aboveformula (II) include carbamoyl chlorides which are well known, such as:

N,N-diethylcarbamoyl chloride,

N-cyclohexyl-N-ethylcarbamoyl chloride,

N,N-di-n-propylcarbamoyl chloride,

N-cyclopropyl-N-n-propylcarbamoyl chloride,

N-cyclopentyl-N-n-propylcarbamoyl chloride,

N-diallylcarbamoyl chloride,

N-dipropargylcarbamoyl chloride,

N-isopropyl-N-phenylcarbamoyl chloride,

N-(2-chlorophenyl)-N-isopropylcarbamoyl chloride,

N-(3-chlorophenyl)-N-isopropylcarbamoyl chloride,

N-(4-chlorophenyl)-N-isopropylcarbamoyl chloride,

N-isopropyl-N-p-tolylcarbamoyl chloride,

N-benzyl-N-isopropylcarbamoyl chloride,

N-(2,3-epoxypropan-1-yl)-N-phenylcarbamoyl chloride,

N-(2-acetylphenyl)-N-isopropylcarbamoyl chloride,

N-isopropyl-N-2-(1-methoxyiminoethyl)phenylcarbamoyl chloride,

1-indolinylcarbonyl chloride,

1,2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride,

2-methyl-1,2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride,

N-(1,1-dimethylpropargyl)-N-phenylcarbamoyl chloride,

N-allyl-N-phenylcarbamoyl chloride,

N-methyl-N-phenylcarbamoyl chloride,

N-ethyl-N-phenylcarbamoyl chloride,

N-n-propyl-N-phenylcarbamoyl chloride,

N-cyclohexyl-N-isopropylcarbamoyl chloride,

N-isopropyl-N-(4-nitrophenyl)carbamoyl chloride,

N-isopropyl-N-(4-cyanophenyl)carbamoyl chloride, etc.

Method is usually carried out in an organic solvent which is inert tothe reaction. Inert organic solvents useful in such a reaction includealiphatic, alicyclic and aromatic hydrocarbons (which may optionally bechlorinated) as exemplified by pentane, hexane, cyclohexane, petroleumether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform,carbon tetrachloride, 1,2-dichloroethane, chlorobenzene anddichlorobenzene; ethers as exemplified by diethyl ether, methyl ethylether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane (DME),tetrahydrofuran (THF) and diethyleneglycol dimethyl ether (DGM); andacid amides as exemplified by dimethyl formamide (DMF), dimethylacetoamide (DMA), N-methyl pyrrolidone, 1,3-dimethyl-2-imidazolidinoneand hexamethyl phosphoric triamide (HMPA).

The process can be carried out in the presence of a base such as4-dimethylamino pyridine (DMAP). DMAP as the base, the process canusually be carried out at a temperature of about -10° to about 200° C.,preferably at about 25° to about 140° C. under atmospheric pressure butit is possible to conduct the reaction under elevated or reducedpressure.

Furthermore, the process can also be conducted using a base other thanDMAP e.g. inorganic bases (such as sodium carbonate, potassiumcarbonate, sodium hydroxide, potassium hydroxide, etc.), alkalialcoholates (such as sodium methoxide, sodium ethoxide, potassiumtert-butoxide, etc.), sodium hydride, potassium hydride, lithiumhydride, organic bases such as triethylamine, 1,1,4,4-tetramethylethylenediamine, N,N-dimethylaniline, pyridine, etc.) and others.

In carrying out such a reaction using any of these bases, the compoundsof formula (I) can be obtained selectively by using DMAP as thecatalyst.

The reaction temperature in such event is usually within the range ofabout 0° to about 150° C., preferably about 25° to about 100° C., and itis preferable to carry out the reaction under atmospheric pressure butoptionally it can also be carried out under elevated or reducedpressure.

Thus, the compounds of formula (I) according to the invention can beproduced by reacting about 1 mole to about 1.5 moles of a compound offormula (III) with 1 mole of a compound of formula (II) in the presenceof about 1 mole to about 1.5 moles of DMAP as the catalyst in an inertsolvent as referred to above. Alternatively, the compounds of formula(I) can be produced by, the reaction of about 1 mole to about 1.5 molesof a compound of formula (III) with 1 mole of a compound of formula (II)in the presence of about 0.01 mole to about 0.3 mole of DMAP as thecatalyst and about 1 mole to about 1.5 moles of, fur example, potassiumcarbonate as the base in an inert solvent as referred to above.

The compounds of formula (I) according to the invention can be isolatedand purified by any means such as crystallization, chromatography, andthe like.

Method b) can be conducted using boron trifluoride ethyl etherate as thecatalyst. The reaction temperature may usually be about 0° to about 200°C., preferably about 50° to about 150° C. and the reaction shouldpreferably be conducted under atmospheric pressure but it is alsopossible to conduct it under elevated or reduced pressure.

Method b) can usually be carried out by reacting about 1 mole to about 2moles of trimethyl silyl azide with 1 mole of the compound of formula(IV) in the presence of about 0.005 mole to about 0.01 mole of borontrifluoride ethyl etherate as the catalyst.

Method c) is usually conducted in a polar solvent such as an acid amide,e.g. dimethyl formamide, dimethyl acetoamide and the like andsulphoxides such as dimethyl sulphoxide, sulpholane,and the like. Thereaction temperature may be set at about 0° to about 200° C. in general,about 20° to about 150° C. preferably and the reaction should preferablybe conducted under atmospheric pressure but it may also be conductedunder elevated or reduced pressure.

Method c) can usually be conducted by reacting about 1 mole to about 1.5moles of sodium azide with 1 mole of the compound of formula IV) in thepresence of about 0.05 mole to about 1 mole of aluminum chloride as thecatalyst in a polar solvent such as dimethyl formamide.

Method d) can be carried out at temperatures of, for instant, about 0 toabout 200° C., preferably about 25° to about 130° C., under atmosphericpressure but it is also possible to carry it out under elevated pressureor reduced pressure.

Method d) can usually be carried out by reacting about 2 moles to about4 moles of trimethyl silyl azide with 1 mole of the compound of formula(V).

Method e) is usually conducted in a solvent which is inert to thereaction, e.g. water and alcohols (such as methanol, ethanol,isopropanol, and the like).

Method e) can be carried out in the presence of, for instance, aninorganic base (such as sodium hydrogen carbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium hydroxide,potassium hydroxide, and the like).

The reaction temperature in method e) can be set usually at about -30°to 50° C., preferably at about 0° to about 30° C. and the reaction ispreferably conducted under atmospheric pressure but it is possible toconduct it under elevated pressure or reduced pressure.

Method e) can usually be carried out by reacting about 1 mole to about1.3 moles of the compound of formula (VII) with 1 mole of the compoundof formula (VI) in the presence of a base in an inert solvent.

The active compounds of formula (I) according to the invention have, asshown in the test examples hereinbelow excellent herbicidal activity sothat they can be used as herbicides for controlling weeds. The term"weeds" in a broad sense means all plants which grow in undesired loci.

The compounds of the invention act either as non-selective or selectiveherbicides depending on the concentration employed. The active compoundsof the invention can be used as selective herbicides between, forexample, the weeds and cultivated plants shown below.

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea,Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium,Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga,Rotala, Lindernia, etc.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita, etc.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena,Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria,Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon,etc.

Monocotyledon cultures of the genera: Oryza, zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium,etc.

However, the use of the active compounds of formula (I) according to theinvention is in no way restricted to the above genera, but also extendsin the same manner to other plants. Further, the active compounds of theinvention are suitable, depending on concentration, for the totalcombating of weeds, for example on industrial terrain, rail tracks, andon paths and squares with or without tree plantings.

Equally, the active compounds of the invention can be employed forcombating weeds in perennial cultures, for example afforestations,decorative tree plantations, orchards, vineyards, citrus groves, nutsorchards, banana plantations, coffee plantations, tea plantations,rubber plantations, oil palm plantations, cocoa plantations, soft fruitplantations and hopfields, and for the selective combating of weeds inannual cultures.

The active compounds of the invention can be converted to the customaryformulations, such as solutions, emulsions, wettable powders,suspensions, powders, soluble powders, dusting agents, granules,tablets, suspension-emulsion concentrates, very fine capsules inpolymeric substances, natural and synthetic materials impregnated withactive compound, etc.

Those formulations are produced in manner known per se, for example, bymixing the active compounds with extenders, that is liquid solventsand/or solid carriers, optionally with the use of surface-active agents,that is emulsifying agents and/or dispersing agents and/or foam-formingagents.

In case of the use of water as an extender, organic solvents can be usedas auxiliary solvents. As liquid solvents, there are suitable in themain: aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes; chlorinated aromatic hydrocarbons and chlorinatedaliphatic hydrocarbons; such as chlorobenzenes, chloroethylenes ormethylene chloride; aliphatic hydrocarbons, such as cyclohexane orparaffins, for example petroleum fractions, mineral and vegetable oils,alcohols, such as butanol or glycol as well as their ethers and esters,ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone; strongly polar solvents, such as dimethylformamide anddimethylsulphoxide.

As solid carriers there are suitable: for example, ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silicic acid, alumina and silicates.As solid carriers for granules there are suitable: for example, crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn and tobacco stalks.

As emulsifying and/or foam-forming agents there are suitable: forexample non-ionic and anionic emulsifiers, such as polyoxyethylene-fattyacid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates aswell as albumin hydrolysis products.

As dispersing agents there are suitable: for example lignin-sulphitewaste liquors and methylcellulose.

Adhesives may also be used optionally in formulations such as powders,granules, natural and synthetic materials impregnated with activecompound or emulsions, and the followings are examples of suchadhesives:

carboxymethylcellulose and natural and synthetic polymers such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids. As further additives there are mineral and vegetableoils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of metals, for exampleiron, manganese, boron, copper, molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weightpreferably between 0.5 and 90% by weight, of the active compound.

The active compounds of formula (I) according to the invention can beused for controlling of weeds as they are or in the form of suchformulations and can be mixed with any known herbicides. The mixture maybe either prepared in advance in the form of a final formulation orprepared by tank-mixing immediately before use.

It is possible to mix the active compounds of formula (I) according tothe invention with a chemical injury-mitigating agent and theapplicability as a selective herbicide can be more broadened by thismixing.

A chemical injury-mitigating agent is exemplified by 1-(α,α-dimethylbenzyl)-3-p-tolyl urea.

The active compounds of formula (I) according to the invention may beapplied by any conventional method such as watering, atomizing, powderspreading or granule scattering.

The active compounds of formula (I) according to the invention may beapplied at any stage of preemergence or postemergence. Also, they can beincorporated into the soil before sowing.

The amount of active compound applied may be varied within a wide rangedepending on the nature of desired effect, the target plants(s) thelocation of application, the time of application, and the like but, as atentative measure, the amount exemplified by about 0.001 kg/ha to about10 kg/ha preferably about 0.01 kg/ha-about 5 kg/ha.

The following examples illustrate the production and uses of thecompounds of the invention, but they should not be regarded as limitingthe invention in any way. The term "part(s)" therein means "part(s) byweight" unless otherwise noted.

EXAMPLES Synthesis Example 1 ##STR16##

1-Cyclopropyl-5(4H)-tetrazolinone (1 g), 4-dimethylaminopyridine (1.1 g)and diethylcarbamoyl chloride (1.2 g) are suspended in toluene (50 ml)and stirred for 5 to 6 hours at 50° to 55° C. After cooling by standing,the organic layer is washed successively with water 1% hydrochloricacid, water, saturated aqueous solution of sodium hydrogen carbonate andwater. After drying of the organic layer over anhydrous sodium sulphate,the solvent is distilled off under reduced pressure and the residue ispurified by column chromatography (eluent: chloroform) to give1-cyclopropyl-4-diethylcarbamoyl-5(4H)-tetrazolinone (1.8 g) n_(D) ²⁰1.5005

The compound obtained in the foregoing Synthesis Example 1, alone withadditional compounds of formula (I) according to the invention,obtainable by the above-mentioned procedure, are shown in the followingTable 1.

                                      TABLE 1                                     __________________________________________________________________________     ##STR17##                                                                    Compound                                    physical                          No.   X.sub.a    R.sup.1      R.sup.2       property                          __________________________________________________________________________    1     --         C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.5005             2     --         "                                                                                           ##STR18##    n.sub.D.sup.20 1.5112             3     --         C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              4     --         "                                                                                           ##STR19##                                      5     --         "                                                                                           ##STR20##                                      6     --         CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                             7     --         CH.sub.2 C CH                                                                              CH.sub.2 C CH                                   8     --         C.sub.3 H.sub.7 -i                                                                          ##STR21##    n.sub.D.sup.20 1.5324             9     --         "                                                                                           ##STR22##                                      10    --         "                                                                                           ##STR23##                                      11    --         "                                                                                           ##STR24##    n.sub.D.sup.20 1.5252             12    --         "                                                                                           ##STR25##    n.sub.D.sup.20 1.5530             13    --         "                                                                                           ##STR26##    mp. 82.5˜83.5°                                                   C.                                14    --         "                                                                                           ##STR27##    mp. 94˜97° C.        15    --         C.sub.3 H.sub.7 -i                                                                          ##STR28##                                      16    --         "                                                                                           ##STR29##                                      17    --         "                                                                                           ##STR30##                                      18    --         "                                                                                           ##STR31##                                      19    --         "                                                                                           ##STR32##                                      20    --         "                                                                                           ##STR33##                                      21    --         "                                                                                           ##STR34##                                      22    --         "                                                                                           ##STR35##                                      23    --         "                                                                                           ##STR36##                                      24    --         "                                                                                           ##STR37##                                      25    --         "                                                                                           ##STR38##                                      26    --         "                                                                                           ##STR39##                                      27    --         "                                                                                           ##STR40##                                      28    --         C.sub.3 H.sub.7 -i                                                                          ##STR41##                                      29    --         "                                                                                           ##STR42##                                      30    --         "                                                                                           ##STR43##                                      31    --         "                                                                                           ##STR44##    mp. 84˜86° C.        32    --         "                                                                                           ##STR45##                                      33    --         "                                                                                           ##STR46##                                      34    --         "                                                                                           ##STR47##                                      35    --         "                                                                                           ##STR48##                                      36    --         "                                                                                           ##STR49##                                      37    --         "                                                                                           ##STR50##    n.sub.D.sup.20 1.5413             38    --         "                                                                                           ##STR51##                                      39    --         "                                                                                           ##STR52##                                      40    --         "                                                                                           ##STR53##    n.sub.D.sup.20 1.5300             41    --         (CH.sub.2).sub.4                                             42    --         (CH.sub.2).sub.3CH(CH.sub.3)                                 43    --                                                                                        ##STR54##                                                   44    --                                                                                        ##STR55##                 n.sub.D.sup.20 1.5678             45    --                                                                                        ##STR56##                 mp. 103˜106° C.      46    --         C(CH.sub.3).sub.2C CH                                                                       ##STR57##    n.sub.D.sup.20 1.5440             47    --         CH(CH.sub.3)C CH                                                                           "             n.sub.D.sup.20 1.5430             48    --         CH.sub.2 C CH                                                                              "                                               49    --         .sub.2 CHCH.sub.2                                                                          "             n.sub.D.sup.20 1.5555             50    --         C.sub.3 H.sub.7 -i                                                                          ##STR58##    n.sub.D.sup.20 1.5317             51    --         C.sub.3 H.sub.7 -n                                                                          ##STR59##    n.sub.D.sup.20 1.5407             52    --         CH.sub.3     "             n.sub.D.sup.20 1.5532             53    --         C.sub.2 H.sub.5                                                                            "             n.sub.D.sup.20 1.5480             54    --         C.sub.4 H.sub.9 -n                                                                         "                                               55    --         C.sub.4 H.sub.9 -sec                                                                       "             n.sub.D.sup.20 1.5345             56    --         C.sub.4 H.sub.9 -iso                                                                       "                                               57    --                                                                                        ##STR60##   "                                               58    --         C(CH.sub.3).sub.2 C CH                                                                      ##STR61##                                      59    --         "                                                                                           ##STR62##                                      60    --         "                                                                                           ##STR63##                                      61    --         C(CH.sub.3).sub.2 C CH                                                                      ##STR64##                                      62    --         "                                                                                           ##STR65##                                      63    --         "                                                                                           ##STR66##    n.sub.D.sup.20 1.5510             64    --         "                                                                                           ##STR67##                                      65    --         "                                                                                           ##STR68##                                      66    --         "                                                                                           ##STR69##                                      67    --         "                                                                                           ##STR70##                                      68    --         CH(CH.sub.3)C CH                                                                            ##STR71##                                      69    --         "                                                                                           ##STR72##                                      70    --         "                                                                                           ##STR73##                                      71    --         "                                                                                           ##STR74##                                      72    --         "                                                                                           ##STR75##                                      73    --                                                                                        ##STR76##                                                                                  ##STR77##    n.sub.D.sup.20 1.5499             74    --         C(CH.sub.3).sub.2 C CH                                                                      ##STR78##                                      75    --         CH(CH.sub.3)C CH                                                                            ##STR79##                                      76    --         C(CH.sub.3).sub.2 C CH                                                                      ##STR80##                                      77    --         "                                                                                           ##STR81##                                      78    --         "                                                                                           ##STR82##                                      79    --         CH(CH.sub.3)C CH                                                                           "                                               80    --         "                                                                                           ##STR83##                                      81    --         C.sub.3 H.sub.7 -i                                                                          ##STR84##                                      82    --         "                                                                                           ##STR85##                                      83    --         "                                                                                           ##STR86##                                      84    --         "                                                                                           ##STR87##                                      85    --         "                                                                                           ##STR88##                                      86    --         "                                                                                           ##STR89##                                      87    --         "                                                                                           ##STR90##                                      88    --         "                                                                                           ##STR91##                                      89    --         "                                                                                           ##STR92##                                      90    --         "                                                                                           ##STR93##                                      91    --         C.sub.3 H.sub.7 -i                                                                          ##STR94##                                      92    --         C(CH.sub.3).sub.2 C CH                                                                      ##STR95##                                      93    --         CH(CH.sub.3)C CH                                                                           "             "                                 94    --         C(CH.sub.3).sub.2 C CH                                                                      ##STR96##                                      95    --         C.sub.3 H.sub.7 -i                                                                          ##STR97##    mp. 87˜90.5° C.      96    1-CH.sub.3 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 97    "          "                                                                                           ##STR98##                                      98    "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              99    "          "                                                                                           ##STR99##                                      100   "          "                                                                                           ##STR100##                                     101   "          CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                             102   "          C.sub.3 H.sub.7 -i                                                                          ##STR101##   n.sub.D.sup.20 1.5148             103   "          "                                                                                           ##STR102##                                     104   "          "                                                                                           ##STR103##   mp. 71˜72.5                 105   "          "                                                                                           ##STR104##                                     106   "          "                                                                                           ##STR105##                                     107   1-CH.sub.3 C.sub.3 H.sub.7 -i                                                                          ##STR106##   mp. 90˜93° C.        108   "          "                                                                                           ##STR107##                                     109   "          "                                                                                           ##STR108##                                     110   "          "                                                                                           ##STR109##                                     111   "          "                                                                                           ##STR110##                                     112   "          "                                                                                           ##STR111##                                     113   "          "                                                                                           ##STR112##                                     114   "          "                                                                                           ##STR113##                                     115   "          "                                                                                           ##STR114##                                     116   "          "                                                                                           ##STR115##                                     117   "          "                                                                                           ##STR116##                                     118   "          "                                                                                           ##STR117##                                     119   "          "                                                                                           ##STR118##                                     120   "          "                                                                                           ##STR119##                                     121   "          (CH.sub.2).sub.4                                             122   1-CH.sub.3 (CH.sub.2).sub.3CH(CH.sub.3)                                 123   "                                                                                         ##STR120##                                                  124   "                                                                                         ##STR121##                                                  125   "                                                                                         ##STR122##                mp. 100˜101° C.      126   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR123##                                     127   "          CH(CH.sub.3)C CH                                                                           "                                               128   "          CH.sub.2 C CH                                                                              "                                               129   "          CH.sub.2 CHCH.sub.2                                                                        "                                               130   "          C.sub.3 H.sub.7 -i                                                                          ##STR124##                                     131   "          C.sub.3 H.sub.7 -n                                                                          ##STR125##                                     132   "          CH.sub.3     "                                               133   "          C.sub.2 H.sub.5                                                                            "                                               134   "          C.sub.4 H.sub.9 -n                                                                         "                                               135   "          C.sub.4 H.sub.9 -sec                                                                       "                                               136   "          C.sub.4 H.sub.9 -i                                                                         "                                               137   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR126##                                     138   1-CH.sub.3 C(CH.sub.3).sub.2 C CH                                                                      ##STR127##                                     139   "          "                                                                                           ##STR128##                                     140   "          "                                                                                           ##STR129##                                     141   "          "                                                                                           ##STR130##                                     142   "          "                                                                                           ##STR131##                                     143   "          "                                                                                           ##STR132##                                     144   "          "                                                                                           ##STR133##                                     145   "          "                                                                                           ##STR134##                                     146   "          CH(CH.sub.3)C CH                                                                            ##STR135##                                     147   "          "                                                                                           ##STR136##                                     148   "          "                                                                                           ##STR137##                                     149   "          "                                                                                           ##STR138##                                     150   "          "                                                                                           ##STR139##                                     151   "          "                                                                                           ##STR140##                                     152   "                                                                                         ##STR141##                                                                                 ##STR142##                                     153   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR143##                                     154   1-CH.sub.3 C(CH.sub.3).sub.2 C CH                                                                      ##STR144##                                     155   "          "                                                                                           ##STR145##                                     156   "          "                                                                                           ##STR146##                                     157   "          CH(CH.sub.3)C CH                                                                            ##STR147##                                     158   "          "                                                                                           ##STR148##                                     159   "          "                                                                                           ##STR149##                                     160   "          C.sub.3 H.sub.7 -i                                                                          ##STR150##                                     161   "          "                                                                                           ##STR151##                                     162   "          "                                                                                           ##STR152##                                     163   "          "                                                                                           ##STR153##                                     164   "          "                                                                                           ##STR154##                                     165   "          "                                                                                           ##STR155##                                     166   "          "                                                                                           ##STR156##                                     167   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR157##                                     168   "          C.sub.3 H.sub.7 -i                                                                          ##STR158##                                     169   1-CH.sub.3 C.sub.3 H.sub.7 -i                                                                          ##STR159##                                     170   "          "                                                                                           ##STR160##                                     171   2-CH.sub.3 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 172   "          "                                                                                           ##STR161##                                     173   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              174   "          "                                                                                           ##STR162##                                     175   "          "                                                                                           ##STR163##                                     176   "          CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                             177   "          C.sub.3 H.sub.7 -i                                                                          ##STR164##   n.sub.D.sup.20 1.5276             178   "          "                                                                                           ##STR165##                                     179   "          "                                                                                           ##STR166##   n.sub.D.sup.20 1.5171             180   "          "                                                                                           ##STR167##                                     181   "          "                                                                                           ##STR168##                                     182   "          "                                                                                           ##STR169##   n.sub.D.sup.20 1.5311             183   "          "                                                                                           ##STR170##                                     184   "          "                                                                                           ##STR171##                                     185   2-CH.sub.3 C.sub.3 H.sub.7 -i                                                                          ##STR172##                                     186   "          "                                                                                           ##STR173##                                     187   "          "                                                                                           ##STR174##                                     188   "          "                                                                                           ##STR175##                                     189   "          "                                                                                           ##STR176##                                     190   "          "                                                                                           ##STR177##                                     191   "          "                                                                                           ##STR178##   n.sub.D.sup.20 1.5207             192   "          "                                                                                           ##STR179##                                     193   "          "                                                                                           ##STR180##                                     194   "          "                                                                                           ##STR181##                                     195   "          "                                                                                           ##STR182##                                     196   "          (CH.sub.2).sub.4                                             197   "          (CH.sub.2).sub.3CH(CH.sub.3)                                 198   "                                                                                         ##STR183##                                                  199   "                                                                                         ##STR184##                                                  200   "                                                                                         ##STR185##                n.sub.D.sup.20 1.5444             201   2-CH.sub.3 C(CH.sub.3).sub.2 C CH                                                                      ##STR186##   n.sub.D.sup.20 1.5289             202   "          CH(CH.sub.3)C CH                                                                           "             n.sub.D.sup.20 1.5353             203   "          CH.sub.2 C CH                                                                              "                                               204   "          CH.sub.2 CHCH.sub.2                                                                        "                                               205   "          C.sub.3 H.sub.7 -i                                                                          ##STR187##   n.sub.D.sup.20 1.5245             206   "          C.sub.3 H.sub.7 -n                                                                          ##STR188##                                     207   "          CH.sub.3     "                                               208   "          C.sub.2 H.sub.5                                                                            "                                               209   "          C.sub.4 H.sub.9 -n                                                                         "                                               210   "          C.sub.4 H.sub.9 -sec                                                                       "                                               211   "          C.sub.4 H.sub.9 -i                                                                          ##STR189##                                     212   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR190##                                     213   "          "                                                                                           ##STR191##                                     214   "          "                                                                                           ##STR192##                                     215   "          "                                                                                           ##STR193##                                     216   "          "                                                                                           ##STR194##                                     217   "          "                                                                                           ##STR195##                                     218   2-CH.sub.3 C(CH.sub.3).sub.2 C CH                                                                      ##STR196##                                     219   "          "                                                                                           ##STR197##                                     220   "          "                                                                                           ##STR198##                                     221   "          "                                                                                           ##STR199##                                     222   "          CH(CH.sub.3)C CH                                                                            ##STR200##                                     223   "          "                                                                                           ##STR201##                                     224   "          "                                                                                           ##STR202##                                     225   "          "                                                                                           ##STR203##                                     226   "          "                                                                                           ##STR204##                                     227   "          "                                                                                           ##STR205##                                     228   "                                                                                         ##STR206##                                                                                 ##STR207##                                     229   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR208##                                     230   "          "                                                                                           ##STR209##                                     231   "          "                                                                                           ##STR210##                                     232   "          "                                                                                           ##STR211##                                     233   "          CH(CH.sub.3)C CH                                                                            ##STR212##                                     234   2-CH.sub.3 CH(CH.sub.3)C CH                                                                            ##STR213##                                     235   "          "                                                                                           ##STR214##                                     236   "          C.sub.3 H.sub.7 -i                                                                          ##STR215##                                     237   "          "                                                                                           ##STR216##                                     238   "          "                                                                                           ##STR217##                                     239   "          "                                                                                           ##STR218##                                     240   "          "                                                                                           ##STR219##                                     241   "          "                                                                                           ##STR220##                                     242   "          "                                                                                           ##STR221##                                     243   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR222##                                     244   "          C.sub.3 H.sub.7 -i                                                                          ##STR223##                                     245   "          "                                                                                           ##STR224##                                     246   "          "                                                                                           ##STR225##                                     247   1,2-(CH.sub.3).sub.2                                                                     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 248   "          "                                                                                           ##STR226##                                     249   1,2-(CH.sub.3).sub.2                                                                     C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              250   "          "                                                                                           ##STR227##                                     251   "          "                                                                                           ##STR228##                                     252   "          C.sub.3 H.sub.7 -i                                                                          ##STR229##                                     253   "          "                                                                                           ##STR230##                                     254   "          "                                                                                           ##STR231##                                     255   "          "                                                                                           ##STR232##                                     256   "          "                                                                                           ##STR233##                                     257   "          "                                                                                           ##STR234##                                     258   "          "                                                                                           ##STR235##                                     259   "          "                                                                                           ##STR236##                                     260   "          "                                                                                           ##STR237##                                     261   "          "                                                                                           ##STR238##                                     262   "          "                                                                                           ##STR239##                                     263   "                                                                                         ##STR240##                                                  264   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR241##                                     265   1,2-(CH.sub.3).sub.2                                                                     CH(CH.sub.3)C CH                                                                            ##STR242##                                     266   "          C.sub.3 H.sub.7 -i                                                                          ##STR243##                                     267   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR244##                                     268   "          "                                                                                           ##STR245##                                     269   "          "                                                                                           ##STR246##                                     270   "          C.sub.3 H.sub.7 -i                                                                          ##STR247##                                     271   2,3-(CH.sub.3).sub.2                                                                     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 272   "          "                                                                                           ##STR248##                                     273   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              274   "          "                                                                                           ##STR249##                                     275   "          "                                                                                           ##STR250##                                     276   "          C.sub.3 H.sub.7 -i                                                                          ##STR251##                                     277   "          "                                                                                           ##STR252##                                     278   "          "                                                                                           ##STR253##                                     279   "          "                                                                                           ##STR254##                                     280   "          "                                                                                           ##STR255##                                     281   2,3-(CH.sub.3).sub.2                                                                     C.sub.3 H.sub.7 -i                                                                          ##STR256##                                     282   "          "                                                                                           ##STR257##                                     283   "          "                                                                                           ##STR258##                                     284   "          "                                                                                           ##STR259##                                     285   "          "                                                                                           ##STR260##                                     286   "          "                                                                                           ##STR261##                                     287   "                                                                                         ##STR262##                                                  288   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR263##                                     289   "          "                                                                                           ##STR264##                                     290   "          "                                                                                           ##STR265##                                     291   "          "                                                                                           ##STR266##                                     292   "          "                                                                                           ##STR267##                                     293   "          CH(CH.sub.3)C CH                                                                            ##STR268##                                     294   "          C.sub.3 H.sub.7 -i                                                                          ##STR269##                                     295   2,2-(CH.sub.3).sub.2                                                                     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 296   "          "                                                                                           ##STR270##                                     297   2,2-(CH.sub.3).sub.2                                                                     C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              298   "          "                                                                                           ##STR271##                                     299   "          "                                                                                           ##STR272##                                     300   "          C.sub.3 H.sub.7 -i                                                                          ##STR273##                                     301   "          "                                                                                           ##STR274##                                     302   "          "                                                                                           ##STR275##                                     303   "          "                                                                                           ##STR276##                                     304   "          "                                                                                           ##STR277##                                     305   "          "                                                                                           ##STR278##                                     306   "          "                                                                                           ##STR279##                                     307   "          "                                                                                           ##STR280##                                     308   "          "                                                                                           ##STR281##                                     309   "          "                                                                                           ##STR282##                                     310   "                                                                                         ##STR283##                                                  311   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR284##                                     312   "          "                                                                                           ##STR285##                                     313   2,2-(CH.sub.3).sub.2                                                                     C(CH.sub.3).sub.2 C CH                                                                      ##STR286##                                     314   "          "                                                                                           ##STR287##                                     315   "          "                                                                                           ##STR288##                                     316   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR289##                                     317   "          "                                                                                           ##STR290##                                     318   1,2,2-(CH.sub.3).sub.3                                                                   C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 319   "          "                                                                                           ##STR291##                                     320   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              321   "          "                                                                                           ##STR292##                                     322   "          "                                                                                           ##STR293##                                     323   "          C.sub.3 H.sub.7 -i                                                                          ##STR294##                                     324   "          "                                                                                           ##STR295##                                     325   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR296##                                     326   1,2,3-(CH.sub.3).sub.3                                                                   C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 327   "          "                                                                                           ##STR297##                                     328   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              329   "          "                                                                                           ##STR298##                                     330   "          "                                                                                           ##STR299##                                     331   1,2,3-(CH.sub.3).sub.3                                                                   C.sub.3 H.sub.7 -i                                                                          ##STR300##                                     332   "          "                                                                                           ##STR301##                                     333   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR302##                                     334   1,2,2,3,3-(CH.sub.3).sub.5                                                               C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 335   "          "                                                                                           ##STR303##   mp. 103˜109° C.      336   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              337   "          "                                                                                           ##STR304##                                     338   "          "                                                                                           ##STR305##                                     339   "          C.sub.3 H.sub.7 -i                                                                          ##STR306##   n.sub.D.sup.20 1.5176             340   "          "                                                                                           ##STR307##                                     341   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR308##                                     342   1-C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 343   "          "                                                                                           ##STR309##                                     344   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              345   "          "                                                                                           ##STR310##                                     346   "          C.sub.3 H.sub.7 -n                                                                          ##STR311##                                     347   "          C.sub.3 H.sub.7 -i                                                                          ##STR312##                                     348   "          "                                                                                           ##STR313##                                     349   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR314##                                     350   2-C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 351   "          "                                                                                           ##STR315##                                     352   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              353   "          "                                                                                           ##STR316##                                     354   "          "                                                                                           ##STR317##                                     355   "          C.sub.3 H.sub.7 -i                                                                          ##STR318##                                     356   "          "                                                                                           ##STR319##                                     357   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR320##                                     358   1-C.sub.2 H.sub.5, 2-CH.sub.3                                                            C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 359   "          "                                                                                           ##STR321##                                     360   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              361   "          "                                                                                           ##STR322##                                     362   "          "                                                                                           ##STR323##                                     363   "          C.sub.3 H.sub.7 -i                                                                          ##STR324##                                     364   "          "                                                                                           ##STR325##                                     365   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR326##                                     366   2-C.sub.2 H.sub.5, 3-CH.sub.3                                                            C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 367   "          "                                                                                           ##STR327##                                     368   "          C.sub.3 H.sub.7 -i                                                                          ##STR328##                                     369   2-C.sub.3 H.sub.7 -n                                                                     C.sub.2 H.sub.5                                                                             ##STR329##                                     370   "          C.sub.3 H.sub.7 -i                                                                          ##STR330##                                     371   2-C.sub.3 H.sub.7 -i                                                                     C.sub.2 H.sub.5                                                                             ##STR331##                                     372   "          C.sub.3 H.sub.7 -i                                                                          ##STR332##                                     373   "          "                                                                                           ##STR333##                                     374   1-C.sub.3 H.sub.7 -i                                                                     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 375   "          "                                                                                           ##STR334##                                     376   "          C.sub.3 H.sub.7 -i                                                                          ##STR335##                                     377   2,2-(CH.sub.3).sub.2, 3-CHCH.sub.2                                                       C.sub.2 H.sub.5                                                                             ##STR336##                                     378   "          C.sub.3 H.sub.7 -i                                                                          ##STR337##                                     379   2,2-(CH.sub.3).sub.2, 3-CHC(CH.sub.3).sub.2                                              C.sub.2 H.sub.5                                                                             ##STR338##   n.sub.D.sup.20 1.5060             380   2,2-(CH.sub.3).sub.2, 3-CHC(CH.sub.3).sub.2                                              C.sub.3 H.sub.7 -i                                                                          ##STR339##   mp. 110˜111.5°                                                   C.                                381   2,2-Cl.sub.2                                                                             C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.5052             382   "          "                                                                                           ##STR340##   n.sub.D.sup.20 1.5163             383   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              384   "          "                                                                                           ##STR341##                                     385   "          "                                                                                           ##STR342##                                     386   "          CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                             387   2,2-Cl.sub.2                                                                             C.sub.3 H.sub.7 -i                                                                          ##STR343##   mp. 131˜134° C.      388   "          "                                                                                           ##STR344##                                     389   "          "                                                                                           ##STR345##                                     390   "          "                                                                                           ##STR346##                                     391   "          "                                                                                           ##STR347##                                     392   "          "                                                                                           ##STR348##                                     393   "          "                                                                                           ##STR349##                                     394   "          "                                                                                           ##STR350##                                     395   "          "                                                                                           ##STR351##                                     396   "          "                                                                                           ##STR352##                                     397   "          "                                                                                           ##STR353##                                     398   "          "                                                                                           ##STR354##                                     399   "          "                                                                                           ##STR355##                                     400   "          "                                                                                           ##STR356##                                     401   2,2-Cl.sub.2                                                                             C.sub.3 H.sub.7 -i                                                                          ##STR357##                                     402   "          "                                                                                           ##STR358##                                     403   "          "                                                                                           ##STR359##                                     404   "          "                                                                                           ##STR360##                                     405   "          "                                                                                           ##STR361##                                     406   "          (CH.sub.2).sub.4                                             407   "          (CH.sub.2).sub.3CH(CH.sub.3)                                 408   "                                                                                         ##STR362##                                                  409   "                                                                                         ##STR363##                                                  410   "                                                                                         ##STR364##                                                  411   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR365##                                     412   "          CH(CH.sub.3)C CH                                                                            ##STR366##                                     413   "          CH.sub.2 C CH                                                                               ##STR367##                                     414   "          CH.sub.2 CHCH.sub.2                                                                         ##STR368##                                     415   "          C.sub.3 H.sub.7 -i                                                                          ##STR369##                                     416   "          C.sub.3 H.sub.7 -n                                                                          ##STR370##                                     417   "          CH.sub.3     "                                               418   2,2-Cl.sub.2                                                                             C.sub.2 H.sub.5                                                                             ##STR371##                                     419   "          C.sub.4 H.sub.9 -n                                                                         "                                               420   "          C.sub.4 H.sub.9 -sec                                                                       "                                               421   "          C.sub.4 H.sub.9 -i                                                                         "                                               422   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR372##                                     423   "          "                                                                                           ##STR373##                                     424   "          "                                                                                           ##STR374##                                     425   "          "                                                                                           ##STR375##                                     426   "          "                                                                                           ##STR376##                                     427   "          "                                                                                           ##STR377##                                     428   "          "                                                                                           ##STR378##                                     429   "          "                                                                                           ##STR379##                                     430   "          "                                                                                           ##STR380##                                     431   "          CH(CH.sub.3)C CH                                                                            ##STR381##                                     432   "          "                                                                                           ##STR382##                                     433   "          "                                                                                           ##STR383##                                     434   2,2-Cl.sub.2                                                                             CH(CH.sub.3)C CH                                                                            ##STR384##                                     435   "          "                                                                                           ##STR385##                                     436   "                                                                                         ##STR386##                                                                                 ##STR387##                                     437   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR388##                                     438   "          "                                                                                           ##STR389##                                     439   "          "                                                                                           ##STR390##                                     440   "          "                                                                                           ##STR391##                                     441   "          CH(CH.sub.3)C CH                                                                            ##STR392##                                     442   "          "                                                                                           ##STR393##                                     443   "          "                                                                                           ##STR394##                                     444   "          C.sub.3 H.sub.7 -i                                                                          ##STR395##                                     445   "          "                                                                                           ##STR396##                                     446   "          "                                                                                           ##STR397##                                     447   "          "                                                                                           ##STR398##                                     448   "          "                                                                                           ##STR399##                                     449   2,2-Cl.sub.2                                                                             C.sub.3 H.sub.7 -i                                                                          ##STR400##                                     450   "          "                                                                                           ##STR401##                                     451   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR402##                                     452   "          C.sub.3 H.sub.7 -i                                                                          ##STR403##                                     453   2,2-Cl.sub.2, 1-CH.sub.3                                                                 C.sub.2 H.sub.5                                                                            C.sub.3 H.sub.7 -i                                                                          n.sub.D.sup.20 1.5003             454   "          "                                                                                           ##STR404##                                     455   2,2-Br.sub.2                                                                             "            C.sub.2 H.sub.5                                 456   "          "                                                                                           ##STR405##                                     457   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              458   "          "                                                                                           ##STR406##                                     459   "          "                                                                                           ##STR407##                                     460   "          C.sub.3 H.sub.7 -i                                                                          ##STR408##                                     461   "          "                                                                                           ##STR409##                                     462   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR410##                                     463   2,2-F.sub.2                                                                              C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 464   "          "                                                                                           ##STR411##                                     465   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              466   2,2-F.sub.2                                                                              C.sub.3 H.sub.7 -n                                                                          ##STR412##                                     467   "          "                                                                                           ##STR413##                                     468   "          C.sub.3 H.sub.7 -i                                                                          ##STR414##   n.sub.D.sup.20 1.5047             469   "          "                                                                                           ##STR415##                                     470   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR416##                                     471   2,2-Cl.sub.2, 1-CH.sub.3                                                                 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.5072             472   "          "                                                                                           ##STR417##   n.sub.D.sup.20 1.5068             473   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              474   "          "                                                                                           ##STR418##                                     475   "          "                                                                                           ##STR419##                                     476   "          C.sub.3 H.sub.7 -i                                                                          ##STR420##   n.sub.D.sup.20 1.5328             477   "          "                                                                                           ##STR421##                                     478   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR422##                                     479   2,2-Cl.sub.2, 1,3-(CH.sub.3).sub.2                                                       C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.5048             480   "          "                                                                                           ##STR423##   n.sub.D.sup.20 1.5276             481   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              482   "          "                                                                                           ##STR424##                                     483   "          "                                                                                           ##STR425##                                     484   2,2-Cl.sub.2, 1,3-(CH.sub.3).sub.2                                                       C.sub.3 H.sub.7 -i                                                                          ##STR426##   n.sub.D.sup.20 1.5223             485   "          "                                                                                           ##STR427##                                     486   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR428##                                     487   2,2-F.sub.2, 1-CH.sub.3                                                                  C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.4653             488   "          "                                                                                           ##STR429##   n.sub.D.sup.20 1.4797             489   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              490   "          "                                                                                           ##STR430##                                     491   "          "                                                                                           ##STR431##                                     492   "          C.sub.3 H.sub.7 -i                                                                          ##STR432##   n.sub.D.sup.20 1.5083             493   "          "                                                                                           ##STR433##                                     494   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR434##                                     495   2,2-Cl.sub.2, 3-CH.sub.3                                                                 C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 496   "          "                                                                                           ##STR435##                                     497   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              498   "          "                                                                                           ##STR436##                                     499   "          "                                                                                           ##STR437##                                     500   "          C.sub.3 H.sub.7 -i                                                                          ##STR438##                                     501   "          "                                                                                           ##STR439##                                     502   2,2-Cl.sub.2, 3-CH.sub.3                                                                 C(CH.sub.3).sub.2 C CH                                                                      ##STR440##                                     503   2,2-Cl.sub.2, 1,3,3-(CH.sub.3).sub.3                                                     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.5016             504   "          "                                                                                           ##STR441##                                     505   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              506   "          "                                                                                           ##STR442##                                     507   "          "                                                                                           ##STR443##                                     508   "          C.sub.3 H.sub.7 -i                                                                          ##STR444##                                     509   "          "                                                                                           ##STR445##                                     510   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR446##                                     511   2,2-Cl.sub.2, 1-C.sub.2 H.sub.5                                                          C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 512   "          "                                                                                           ##STR447##                                     513   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              514   "          "                                                                                           ##STR448##                                     515   "          "                                                                                           ##STR449##                                     516   "          C.sub.3 H.sub.7 -i                                                                          ##STR450##                                     517   "          "                                                                                           ##STR451##                                     518   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR452##                                     519   2-Cl, 2-F  C.sub.2 H.sub.5                                                                             ##STR453##                                     520   2-Cl, 2-F  C.sub.3 H.sub.7 -i                                                                          ##STR454##   n.sub.D.sup.20 1.5194             521   2-Cl, 2-F, 1-CH.sub.3                                                                    C.sub.2 H.sub.5                                                                             ##STR455##                                     522   "          C.sub.3 H.sub.7 -i                                                                          ##STR456##                                     523   2,2-Br.sub.2, 1-CH.sub.3                                                                 C.sub.2 H.sub.5                                                                             ##STR457##                                     524   "          C.sub.3 H.sub.7 -i                                                                          ##STR458##                                     525   2,2-Br.sub.2, 1,3-(CH.sub.3).sub.2                                                       C.sub.2 H.sub.5                                                                             ##STR459##                                     526   2,2-Cl.sub.2, 1-C.sub.2 H.sub.5, 3-CH.sub.3                                              "            "                                               527   2,2-Cl.sub.2, 1-C.sub.3 H.sub.7 -i                                                       C.sub.3 H.sub.7 -i                                                                          ##STR460##                                     528   2,2-F.sub.2                                                                              CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                             529   "          CH.sub.2 C CH                                                                              CH.sub.2 C CH                                   530   "          C.sub.3 H.sub.7 -i                                                                          ##STR461##                                     531   "          "                                                                                           ##STR462##                                     532   "          "                                                                                           ##STR463##   n.sub.D.sup.20 1.4996             533   "          "                                                                                           ##STR464##                                     534   "          "                                                                                           ##STR465##                                     535   "          "                                                                                           ##STR466##   n.sub.D.sup.20 1.5203             536   2,2-F.sub.2                                                                              C.sub.3 H.sub.7 -i                                                                          ##STR467##                                     537   "          "                                                                                           ##STR468##                                     538   "          "                                                                                           ##STR469##                                     539   "          "                                                                                           ##STR470##                                     540   "          "                                                                                           ##STR471##                                     541   "          "                                                                                           ##STR472##                                     542   "          "                                                                                           ##STR473##                                     543   "          "                                                                                           ##STR474##                                     544   "          "                                                                                           ##STR475##                                     545   "          "                                                                                           ##STR476##                                     546   "          "                                                                                           ##STR477##                                     547   "          "                                                                                           ##STR478##                                     548   "          "                                                                                           ##STR479##                                     549   "          "                                                                                           ##STR480##                                     550   2,2-F.sub.2                                                                              C.sub.3 H.sub.7 -i                                                                          ##STR481##                                     551   "          "                                                                                           ##STR482##                                     552   "          "                                                                                           ##STR483##                                     553   "          "                                                                                           ##STR484##                                     554   "          (CH.sub.2).sub.4                                             555   "          (CH.sub.2).sub.3CH(CH.sub.3)                                 556   "                                                                                         ##STR485##                                                  557   "                                                                                         ##STR486##                                                  558   "                                                                                         ##STR487##                n.sub.D.sup.20 1.5343             559   "          CH(CH.sub.3)C CH                                                                            ##STR488##                                     560   "          CH.sub.2 C CH                                                                              "                                               561   "          C.sub.3 H.sub.7 -i                                                                          ##STR489##                                     562   "          C.sub.3 H.sub.7 -n                                                                          ##STR490##                                     563   "          CH.sub.3     "                                               564   "          C.sub.2 H.sub.5                                                                            "             n.sub.D.sup.20 1.5188             565   "          C.sub.4 H.sub.9 -n                                                                         "                                               566   2,2-F.sub.2                                                                              C.sub.4 H.sub.9 -sec                                                                        ##STR491##                                     567   "          C.sub.4 H.sub.9 -i                                                                         "                                               568   "                                                                                         ##STR492##  "                                               569   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR493##                                     570   "          "                                                                                           ##STR494##                                     571   "          "                                                                                           ##STR495##                                     572   "          "                                                                                           ##STR496##                                     573   "          "                                                                                           ##STR497##                                     574   "          "                                                                                           ##STR498##                                     575   "          "                                                                                           ##STR499##                                     576   "          "                                                                                           ##STR500##                                     577   "          "                                                                                           ##STR501##                                     578   "          "                                                                                           ##STR502##                                     579   "          CH(CH.sub.3)C CH                                                                            ##STR503##                                     580   "          "                                                                                           ##STR504##                                     581   "          "                                                                                           ##STR505##                                     582   2,2-F.sub.2                                                                              CH(CH.sub.3)C CH                                                                            ##STR506##                                     583   "          "                                                                                           ##STR507##                                     584   "          "                                                                                           ##STR508##                                     585   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR509##                                     586   "          "                                                                                           ##STR510##                                     587   "          CH(CH.sub.3)C CH                                                                            ##STR511##                                     588   "          "                                                                                           ##STR512##                                     589   "          "                                                                                           ##STR513##                                     590   "          C.sub.3 H.sub.7 -i                                                                          ##STR514##                                     591   "          "                                                                                           ##STR515##                                     592   "          "                                                                                           ##STR516##                                     593   "          "                                                                                           ##STR517##                                     594   "          "                                                                                           ##STR518##                                     595   "          "                                                                                           ##STR519##                                     596   "          "                                                                                           ##STR520##                                     597   2,2-F.sub.2                                                                              C.sub.3 H.sub.7 -i                                                                          ##STR521##                                     598   "          "                                                                                           ##STR522##                                     599   "          "                                                                                           ##STR523##                                     600   "          "                                                                                           ##STR524##                                     601   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR525##                                     602   "          CH(CH.sub.3)C CH                                                                           "                                               603   2,2-F.sub.2, 1-CH.sub.3                                                                  CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                             604   "          CH.sub.2 C CH                                                                              CH.sub.2 C CH                                   605   "          C.sub.3 H.sub.7 -i                                                                          ##STR526##                                     606   "          "                                                                                           ##STR527##                                     607   "          "                                                                                           ##STR528##   n.sub.D.sup.20 1.4893             608   "          "                                                                                           ##STR529##                                     609   "          "                                                                                           ##STR530##                                     610   "          "                                                                                           ##STR531##   n.sub.D.sup.20 1.5095             611   "          "                                                                                           ##STR532##                                     612   2,2-F.sub.2, 1-CH.sub.3                                                                  C.sub.3 H.sub.7 -i                                                                          ##STR533##                                     613   "          "                                                                                           ##STR534##                                     614   "          "                                                                                           ##STR535##                                     615   "          "                                                                                           ##STR536##                                     616   "          "                                                                                           ##STR537##                                     617   "          "                                                                                           ##STR538##                                     618   "          "                                                                                           ##STR539##                                     619   "          "                                                                                           ##STR540##                                     620   "          "                                                                                           ##STR541##                                     621   "          "                                                                                           ##STR542##                                     622   "          "                                                                                           ##STR543##                                     623   "          "                                                                                           ##STR544##                                     624   "          "                                                                                           ##STR545##                                     625   "          "                                                                                           ##STR546##                                     626   2,2-F.sub.2, 1-CH.sub.3                                                                  C.sub.3 H.sub.7 -i                                                                          ##STR547##                                     627   "          "                                                                                           ##STR548##                                     628   "          "                                                                                           ##STR549##                                     629   "          (CH.sub.2).sub.4                                             630   "          (CH.sub.2).sub.3CH(CH.sub.3)                                 631   "                                                                                         ##STR550##                                                  632   "                                                                                         ##STR551##                                                  633   "                                                                                         ##STR552##                n.sub.D.sup.20 1.5067             634   "          CH(CH.sub.3)C CH                                                                            ##STR553##                                     635   "          CH.sub.2 C CH                                                                              "                                               636   "          C.sub.3 H.sub.7 -i                                                                          ##STR554##                                     637   "          C.sub.3 H.sub.7 -n                                                                          ##STR555##                                     638   "          CH.sub.3     "                                               639   "          C.sub.2 H.sub.5                                                                            "                                               640   "          C.sub.4 H.sub.9 -n                                                                         "                                               641   "          C.sub.4 H.sub.9 -sec                                                                       "                                               642   "          C.sub.4 H.sub.9 -i                                                                         "                                               643   2,2-F.sub.2, 1-CH.sub.3                                                                   ##STR556##                                                                                 ##STR557##                                     644   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR558##                                     645   "          "                                                                                           ##STR559##                                     646   "          "                                                                                           ##STR560##                                     647   "          "                                                                                           ##STR561##                                     648   "          "                                                                                           ##STR562##                                     649   "          "                                                                                           ##STR563##                                     650   "          "                                                                                           ##STR564##                                     651   "          "                                                                                           ##STR565##                                     652   "          "                                                                                           ##STR566##                                     653   "          "                                                                                           ##STR567##                                     654   "          CH(CH.sub.3)C CH                                                                            ##STR568##                                     655   "          "                                                                                           ##STR569##                                     656   "          "                                                                                           ##STR570##                                     657   "          "                                                                                           ##STR571##                                     658   "          "                                                                                           ##STR572##                                     659   2,2-F.sub.2, 1-CH.sub.3                                                                  CH(CH.sub.3)C CH                                                                            ##STR573##                                     660   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR574##                                     661   "          "                                                                                           ##STR575##                                     662   "          CH(CH.sub.3)C CH                                                                            ##STR576##                                     663   "          "                                                                                           ##STR577##                                     664   "          "                                                                                           ##STR578##                                     665   "          C.sub.3 H.sub.7 -i                                                                          ##STR579##                                     666   "          "                                                                                           ##STR580##                                     667   "          "                                                                                           ##STR581##                                     668   "          "                                                                                           ##STR582##                                     669   "          "                                                                                           ##STR583##                                     670   "          "                                                                                           ##STR584##                                     671   "          "                                                                                           ##STR585##                                     672   "          "                                                                                           ##STR586##                                     673   "          "                                                                                           ##STR587##                                     674   2,2-F.sub.2, 1-CH.sub.3                                                                  C.sub.3 H.sub.7 -i                                                                          ##STR588##                                     675   "          "                                                                                           ##STR589##                                     676   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR590##                                     677   "          CH(CH.sub.3)C CH                                                                           "                                               678   2-Cl, 2-F  CH.sub.2 CHCH.sub.2                                                                        CH.sub.2 CHCH.sub.2                             679   "          CH.sub.2 C CH                                                                              CH.sub.2 C CH                                   680   "          C.sub.3 H.sub.7 -i                                                                          ##STR591##                                     681   "          "                                                                                           ##STR592##                                     682   "          "                                                                                           ##STR593##   n.sub.D.sup.20 1.5155             683   "          "                                                                                           ##STR594##                                     684   "          "                                                                                           ##STR595##                                     685   "          "                                                                                           ##STR596##                                     686   "          "                                                                                           ##STR597##                                     687   "          "                                                                                           ##STR598##                                     688   "          "                                                                                           ##STR599##                                     689   2-Cl, 2-F  C.sub.3 H.sub.7 -i                                                                          ##STR600##                                     690   "          "                                                                                           ##STR601##                                     691   "          "                                                                                           ##STR602##                                     692   "          "                                                                                           ##STR603##                                     693   "          "                                                                                           ##STR604##                                     694   "          "                                                                                           ##STR605##                                     695   "          "                                                                                           ##STR606##                                     696   "          "                                                                                           ##STR607##                                     697   "          "                                                                                           ##STR608##                                     698   "          "                                                                                           ##STR609##                                     699   "          "                                                                                           ##STR610##                                     700   "          "                                                                                           ##STR611##                                     701   "          "                                                                                           ##STR612##                                     702   "          "                                                                                           ##STR613##                                     703   "          "                                                                                           ##STR614##                                     704   2,Cl, 2-F  (CH.sub.2).sub.4                                             705   "          (CH.sub.2).sub.3CH(CH.sub.3)                                 706   "                                                                                         ##STR615##                                                  707   "                                                                                         ##STR616##                                                  708   "                                                                                         ##STR617##                mp. 65˜70° C.        709   "          CH(CH.sub.3)C CH                                                                            ##STR618##                                     710   "          CH.sub.2 C CH                                                                              "                                               711   "          C.sub.3 H.sub.7 -i                                                                          ##STR619##                                     712   "          C.sub.3 H.sub.7 -n                                                                          ##STR620##                                     713   "          CH.sub.3     "                                               714   "          C.sub.2 H.sub.5                                                                            "                                               715   "          C.sub.4 H.sub.9 -n                                                                         "                                               716   "          C.sub.4 H.sub.9 -sec                                                                       "                                               717   "          C.sub.4 H.sub.9 -i                                                                         "                                               718   "                                                                                         ##STR621##  "                                               719   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR622##                                     720   2-Cl, 2-F  C(CH.sub.3).sub.2 C CH                                                                      ##STR623##                                     721   "          "                                                                                           ##STR624##                                     722   "          "                                                                                           ##STR625##                                     723   "          "                                                                                           ##STR626##                                     724   "          "                                                                                           ##STR627##                                     725   "          "                                                                                           ##STR628##                                     726   "          "                                                                                           ##STR629##                                     727   "          "                                                                                           ##STR630##                                     728   "          "                                                                                           ##STR631##                                     729   "          CH(CH.sub.3)C CH                                                                            ##STR632##                                     730   "          "                                                                                           ##STR633##                                     731   "          "                                                                                           ##STR634##                                     732   "          "                                                                                           ##STR635##                                     733   "          "                                                                                           ##STR636##                                     734   "          "                                                                                           ##STR637##                                     735   2-Cl, 2-F  C(CH.sub.3).sub.2 C CH                                                                      ##STR638##                                     736   "          "                                                                                           ##STR639##                                     737   "          CH(CH.sub.3)C CH                                                                            ##STR640##                                     738   "          "                                                                                           ##STR641##                                     739   "          "                                                                                           ##STR642##                                     740   "          C.sub.3 H.sub.7 -i                                                                          ##STR643##                                     741   "          "                                                                                           ##STR644##                                     742   "          "                                                                                           ##STR645##                                     743   "          "                                                                                           ##STR646##                                     744   "          "                                                                                           ##STR647##                                     745   "          "                                                                                           ##STR648##                                     746   "          "                                                                                           ##STR649##                                     747   "          "                                                                                           ##STR650##                                     748   "          "                                                                                           ##STR651##                                     749   "          "                                                                                           ##STR652##                                     750   2,Cl, 2-F  C.sub.3 H.sub.7 -i                                                                          ##STR653##                                     751   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR654##                                     752   "          CH(CH.sub.3)C CH                                                                           "                                               753   2-F        C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 754   "          "                                                                                           ##STR655##                                     755   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              756   "          "                                                                                           ##STR656##                                     757   "          "                                                                                           ##STR657##                                     758   "          C.sub.3 H.sub.7 -i                                                                          ##STR658##   n.sub.D.sup.20 1.5210             759   "          "                                                                                           ##STR659##                                     760   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR660##                                     761   "          CH(CH.sub.3)C CH                                                                           "                                               762   "          "                                                                                           ##STR661##                                     763   "          "                                                                                           ##STR662##                                     764   "          C.sub.3 H.sub.7 -i                                                                          ##STR663##                                     765   "          "                                                                                           ##STR664##   mp. 67˜69° C.        766   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR665##                                     767   "          "                                                                                           ##STR666##                                     768   "          "                                                                                           ##STR667##                                     769   2-F, 1-CH.sub.3                                                                          C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                 770   "          "                                                                                           ##STR668##                                     771   "          C.sub.3 H.sub.7 -n                                                                         C.sub.3 H.sub.7 -n                              772   "          "                                                                                           ##STR669##                                     773   "          "                                                                                           ##STR670##                                     774   "          C.sub.3 H.sub.7 -i                                                                          ##STR671##   n.sub.D.sup.20 1.5149             775   "          "                                                                                           ##STR672##                                     776   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR673##                                     777   "          CH(CH.sub.3)C CH                                                                           "                                               778   "          "                                                                                           ##STR674##                                     779   "          "                                                                                           ##STR675##                                     780   "          C.sub.3 H.sub.7 -i                                                                          ##STR676##                                     781   "          "                                                                                           ##STR677##   n.sub.D.sup.20 1.5103             782   "          C(CH.sub.3).sub.2 C CH                                                                      ##STR678##                                     783   "          "                                                                                           ##STR679##                                     784   "          "                                                                                           ##STR680##                                     785   --                                                                                        ##STR681##                n.sub.D.sup.20 1.5749             786   --                                                                                        ##STR682##                n.sub.D.sup.20 1.5602             787   --         C.sub.3 H.sub.7 -i                                                                         CH.sub.3                                        788   --         "            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.4938             789   2,2-Cl.sub.2                                                                             "            CH.sub.3                                        790   "          "            C.sub.2 H.sub.5                                 791   2,2-F.sub.2, 1-CH.sub.3                                                                  "            CH.sub.3                                        792   "          "            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.4655             793   2,2-F.sub.2                                                                              "            CH.sub.3                                        794   "          "            C.sub.2 H.sub.5                                                                             n.sub.D.sup.20 1.4670             795   1-CH.sub.3 "            "                                               796   2-CH.sub.3 "            "                                               797   2,2-Cl.sub.2, 1-CH.sub.3                                                                 "            CH.sub.3                                        798   --                                                                                        ##STR683##                                                                                 ##STR684##                                     799   2,2-Cl.sub.2, 1,2-(CH.sub.3).sub.2                                                       C.sub.3 H.sub.7 -i                                                                         CH.sub.3                                        800   "          "            C.sub.2 H.sub.5                                 801   1-Cl       "                                                                                           ##STR685##   n.sub.D.sup.20 1.5318             802   --         "            CH.sub.2 CHCH.sub.2                             803   2,2-F.sub.2                                                                              "            "                                               804   2,2-F.sub.2, 1-CH.sub.3                                                                  CH.sub.2 CHCH.sub.2                                                                        "                                               805   --                                                                                        ##STR686##                                                                                 ##STR687##                                     806   2-F, 1-CH.sub.3                                                                          C.sub.3 H.sub.7 -i                                                                         C.sub.2 H.sub.5                                 807   2-F        "            "                                               808   2-Cl, 2-F  "            "             n.sub.D.sup.20 1.4821             809   --         CH(CH.sub.3)(CH.sub.2).sub.3CH(CH.sub.3)                                                                 mp. 109˜112° C.      810   1-CH.sub.3 "                                                            811   2-CH.sub.3 "                                                            812   2,2-F.sub.2                                                                              "                                                            813   --         CH(CH.sub.3)(CH.sub.2).sub.2CH(CH.sub.3)                     814   1-CH.sub.3 "                                                            815   2-CH.sub.3 "                                                            816   2-F        "                                                            817   --                                                                                        ##STR688##                mp. 134˜135° C.      818   1-CH.sub.3 "                                                            819   2-CH.sub.3 "                                                            820   --                                                                                        ##STR689##                                                  821   --                                                                                        ##STR690##                n.sub.D.sup.20 1.5928             822   1-CH.sub.3 "                                                            823   2-CH.sub.3 "                                                            824   2,2-F.sub.2, 1-CH.sub.3                                                                  "                                                            825   --                                                                                        ##STR691##                mp. 130˜131° C.      826   1-CH.sub.3 "                                                            827   2-CH.sub.3 "                                                            828   2,2-F.sub.2                                                                              "                                                            829   2,2-F.sub.2, 1-CH.sub.3                                                                  "                                                            830   2-F                                                                                       ##STR692##                n.sub.D.sup.20 1.5444             831   2-F.sub.2, 1-CH.sub.3                                                                    "                          mp. 91˜96° C.        832   --                                                                                        ##STR693##                                                  833   --                                                                                        ##STR694##                mp. 116˜118° C.      834   --                                                                                        ##STR695##                                                  835   --                                                                                        ##STR696##                                                  836   --                                                                                        ##STR697##                                                  837   --                                                                                        ##STR698##                                                  838   --                                                                                        ##STR699##                                                  839   --                                                                                        ##STR700##                n.sub.D.sup.20 1.5515             840   1-CH.sub.3 "                          mp. 86˜89° C.        841   2-CH.sub.3 "                          n.sub.D.sup.20 1.5498             842   2,2-F.sub.2                                                                              "                                                            843   2,2-F.sub.2, 1-CH.sub.3                                                                  "                                                            844   2,2-(CH.sub.3).sub.2                                                                     "                                                            845   2,2-Cl.sub.2                                                                             "                                                            846   2-Cl, 2-F  "                                                            847   --                                                                                        ##STR701##                                                  848   --                                                                                        ##STR702##                                                  849   --                                                                                        ##STR703##                n.sub.D.sup.20 1.5450             850   --                                                                                        ##STR704##                mp. 117.5˜120.5°                                                 C.                                851   1-CH.sub.3                                                                                ##STR705##                mp. 94.5˜96.5°                                                   C.                                852   2-CH.sub.3                                                                                ##STR706##                n.sub.D.sup.20 1.5549             853   2,2-F.sub.2                                                                              "                                                            854   2,2-F.sub.2, 1-CH.sub.3                                                                  "                          n.sub.D.sup.20 1.5254             855   2-Cl, 2-F  "                                                            856   2-F        "                                                            857   2-F, 1-CH.sub.3                                                                          "                                                            858   --                                                                                        ##STR707##                                                  859   --                                                                                        ##STR708##                n.sub.D.sup.20 1.5568             860   2,2-F.sub.2, 1-CH.sub.3                                                                  "                                                            861   --                                                                                        ##STR709##                                                  862   1-CH.sub.3                                                                                ##STR710##                                                  863   2-CH.sub.3 "                                                            864   --                                                                                        ##STR711##                mp. 111˜113.5°                                                   C.                                865   --                                                                                        ##STR712##                                                  866   --                                                                                        ##STR713##                                                  867   --                                                                                        ##STR714##                                                  868   --                                                                                        ##STR715##                                                  869   --                                                                                        ##STR716##                n.sub.D.sup.20 1.5603             870   --                                                                                        ##STR717##                                                  871   --                                                                                        ##STR718##                                                  872   --                                                                                        ##STR719##                                                  873   2,2-F.sub.2, 1-CH.sub.3                                                                   ##STR720##                                                  __________________________________________________________________________

Synthesis Example 2

(Synthesis of an intermediate) ##STR721##

Cyclopropyl isocyanate (10 g), trimethylsilyl azide (20.8 g) and acatalytic amount of boron trifluoride ethyl etherate are mixed andheated for 40 hours with refluxing. The excess trimethylsilyl azide isdistilled off under reduced pressure, methanol is added to the residueand then methanol is distilled off under reduced pressure. Purifying theresidue by column chromatography (eluent:ethanol/chloroform=6/100) givescyclopropyl-5(4H)-tetrazolinone (12.0 g). m.p. 100°-104° C.

Synthesis Example 3

(Synthesis of an intermediate) ##STR722##

2,2-Dichlorocyclopropanecarbonyl chloride (10 g), trimethylsilyl azide(20.0 g) and a catalytic amount of boron trifluoride ethyl etherate aremixed and heated for 48 hours with refluxing. The excess trimethylsilylazides is distilled off under reduced pressure, methanol is added to theresidue and then methanol is distilled off under reduced pressure.Purifying the residue by column chromatography(eluent:ethanol/chloroform=6/100 gives1-(2,2-dichlorocyclopropyl)-5(4H)-tetrazolinone (8.5 g). m.p. 109°-112°C.

The compounds obtained in the foregoing Synthesis Examples 2 and 3 alongwith additional compounds of formula (II), obtainable by a methodcorresponding to that used in the above Synthesis Examples 2 and 3, areshown in the following Table 2.

                  TABLE 2                                                         ______________________________________                                         ##STR723##                                                                   Compound                                                                      No.       X.sub.a           physical property                                 ______________________________________                                        2.1       --                mp. 100˜104° C.                      2.2       2-CH.sub.3        n.sub.D.sup.20 1.4906                             2.3       1-CH.sub.3        n.sub.D.sup.20 1.4634                             2.4       2,2-(CH.sub.3).sub.2                                                2.5       2,3-(CH.sub.3).sub.2                                                2.6       1,2-(CH.sub.3).sub.2                                                2.7       1,2,2-(CH.sub.3).sub.3                                              2.8       1,2,3-(CH.sub.3).sub.3                                              2.9       2,2,3,3-(CH.sub.3).sub.4                                                                        mp. 110˜112° C.                      2.10      1-C.sub.2 H.sub.5                                                   2.11      2-C.sub.2 H.sub.5                                                   2.12      1-C.sub.2 H.sub.5, 2-CH.sub.3                                       2.13      2-C.sub.2 H.sub.5, 3-CH.sub.3                                       2.14      2-C.sub.3 H.sub.7 -n                                                2.15      2-C.sub.3 H.sub.7 -i                                                2.16      1-C.sub.3 H.sub.7 -i                                                2.17      2,2-(CH.sub.3).sub.2, 1-CHCH.sub.2                                  2.18      2,2-(CH.sub.3).sub.2, 1-CHC(CH.sub.3).sub.2                                                     mp. 99˜102° C.                       2.19      2,2-Cl.sub.2      mp. 109˜112° C.                      2.20      2,2-Br.sub.2                                                        2.21      2,2-F.sub.2       n.sub.D.sup.20 1.4443                             2.22      2-Cl, 2-F         n.sub.D.sup.20 1.4761                             2.23      2-Cl, 2-F, 1-CH.sub.3                                               2.24      2,2-Br.sub.2, 1-CH.sub.3                                            2.25      2,2-Br.sub.2, 1,3-(CH.sub.3).sub.2                                  2.26      2,2-Cl.sub.2, 1-CH.sub.3                                                                        mp. 129˜132° C.                      2.27      2,2-Cl.sub.2, 1,3-(CH.sub.3).sub.2                                  2.28      2,2-F.sub.2, 1-CH.sub.3                                                                         mp. 75˜78.5° C.                      2.29      2,2-Cl.sub.2, 3-CH.sub.3                                            2.30      2,2-Cl.sub.2, 1,3,3-(CH.sub.3).sub.3                                                            mp. 100˜104° C.                      2.31      2,2-Cl.sub.2, 1-C.sub.2 H.sub.5                                     2.32      2,2-Cl.sub.2, 1-C.sub.2 H.sub.5, 3-CH.sub.3                         2.33      2,2-Cl.sub.2, 1-C.sub.3 H.sub.7 -i                                  2.34      2-F               n.sub.D.sup.20 1.4778                             2.35      2-F, 1-CH.sub.3   mp. 128˜131° C.                      2.36      1-Cl              mp. 55˜58° C.                        ______________________________________                                    

Test Example 1

Pre-emergence soil treatment test against plowed land weeds

Method of preparation:

carrier: acetone, 5 parts by weight

emulsifying agent; benzyloxypolyglycol ether, 1 part by weight

An emulsion is obtained by mixing 1 part by weight of the activecompound with the above amounts of carrier and emulsifying agent. Aportion of this emulsion containing a prescribed amount of the chemicalis diluted with water to prepare the formulation for testing.

Testing Method:

In the greenhouse, seeds of Echinochloa and Amaranthus lividus weresowed in the surface layer of plowed land soil filled in a 120 cm² potwith soil-covering and the above formulated in a 120 cm² pot withsoil-covering and the above formulated chemical was uniformly spread onthe surface layer of soil in the test pot in prescribed amount of thechemical. 4 weeks after spreading, the herbicidal effect was examined.The herbicidal effect was rated as 100% for complete death and as 0% foruntreated pots.

Result:

The weeds were 100% killed by application of 1 kg/ha of compounds Nos.1, 2, 8, 12, 13, 14, 31, 46, 50, 51, 63, 102, 177, 488 and 492.

Test Example 2

Post-emergence foliage treatment test against plowed land weeds

Testing Method:

In the greenhouse, seeds of Echinochloa and Amaranthus lividus weresowed in a 120 cm² pot filled with plowed land soil and covered withsoil. 10 Days after sowing (when the weeds on average in the a-leafstage, the formulated chemical prepared similarly to foregoing TestExample 1 was uniformly spread on the foliage of the test plant in eachtest pot in prescribed amount. 3 weeks after spreading the herbicidaleffect was examined.

Result:

90% or more of the weeds were killed by application of 2 kg/ha ofCompounds Nos. 8, 12, 13, 31, 46, 63, 102, 177 and 492.

Formulation Example 1

(granules)

Twenty-five parts of water are added to a mixture of 10 parts ofCompound No. 8, 30 parts of bentonite (montmorillonite), 58 parts oftalc and 2 parts of lignin sulphonic acid salt to be well kneadedfollowed by granulating to 10-40 mesh granules using an extrusion typegranulation and drying at 40°-50° C.

Formulation Example 2

(granules)

A rotary mixer is charged with 95 parts of clay mineral granules havinga particle size distribution within the range of 0.2-2 mm and 5 parts ofCompound No. 102 is sprayed therein with a liquid diluent undercontinuous rotation for uniformly wetting, followed by drying at 40°-50°C.

Formulation Example 4

(granules)

An emulsion is obtained by mixing and stirring 30 parts of Compound No.8, 55 parts of xylene, 8 parts of polyoxyethelene alkylphenyl ether and7 parts of calcium alkylbenzene sulphonate.

Formulation Example 4

(wettable powder)

A wettable powder is obtained by grinding and mixing 15 parts ofCompound No. 31, 80 parts of a mixture of White Carbon (fine powder ofhydrated non-crystalline silicon oxide) and powdery clay (1:5), 2 partsof sodium alkylbenzene sulphonate and 3 parts of a condensate of sodiumalkylnaphthalene sulphonate with formaldehyde.

Formulation Example 5

(wettable granules)

Twenty parts of Compound No. 46, 30 parts of sodium lignin sulphonate,15 parts of bentonite and 35 parts of calcined diatomaceous earth powderare mixed and water is added to the mixture followed by extrusionthrough a 0.3 mm screen and drying to give wettable granules.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiment within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A 1-cyclopropyl tetrazolinone of the formula ##STR724## wherein X represent C₁₋₃ alkyl, C₂₋₄ alkenyl or halogen,n represent 0 to 5, R¹ and R² each independently represents C₁₋₆ -alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₇ cycloalkyl which may optionally be substituted by C₁₋₃ alkyl, epoxy-C₃₋₅ alkan-1-yl, optionally substituted phenyl, optionally substituted benzyl, optionally substituted 1-phenylethyl and optionally substituted 2-phenylethyl wherein the substituents are selected from the group consisting of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, C₁₋₄ haloalkylthio, cyano, nitro, C₁₋₄ alkylcarbonyl, C₁₋₄ alkoxycarbonyl, and alkoxyimino-C₁₋₂ -alkyl, or R¹ and R² together with the N-atom to which they are attached, represent an optionally methyl or ethyl substituted cyclic ring wherein said ring is selected from the group consisting of pyrrolidin-1-yl, indol-1-yl, indolin-1-yl, 1,2-dihydroquinolin-1-yl, and 1,2,3,4-tetrahydroquinolin 1-yl.
 2. A compound according to claim 1, whereinX represents methyl, ethyl, vinyl, allyl, 1-propenyl, fluorine, chlorine, or bromine, n represents 0 to 4, and R¹ and R² each independently represents C₁₋₄ alkyl, C₃₋₅ alkenyl, C₃₋₅ alkynyl, C₃₋₆ cycloalkyl which may optionally be substituted by methyl, 2,3-epoxypropan-1-yl, phenyl which may optionally be substituted or benzyl which may optionally be substituted, the optional substituents on said phenyl or said benzyl being independently selected from the group consisting of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₂ haloalkyl, C₁₋₂ haloalkoxy, C₁₋₄ alkylthio, C₁₋₂ haloalkylthio, cyano, nitro, C₁₋₂ alkylcarbonyl and C₁₋₂ alkoxy-imino-C₁₋₂ alkyl, or R¹ and R² together with the N-atom to which they are attached, represent pyrrolidin-1-yl, indol-1-yl, indolin-1-yl, 1,2-dihydroquinolin-1-yl or 1,2,3,4-tetrahydroquinolin-1-yl which may optionally be substituted by methyl.
 3. A compound according to claim 1, whereinX represents methyl, ethyl, fluorine or chlorine, n represents 0 to 4, and R¹ and R² each independently represents C₁₋₃ alkyl, C₃₋₅ alkyl, C₃₋₅ alkynyl, cyclopropyl, cyclopentyl, cyclohexyl which may optionally be substituted by methyl, 2,3-epoxypropan-1-yl, phenyl which may optionally be substituted or benzyl which may optionally be substituted the optional substituents on said phenyl or said benzyl being independently selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethylthio, cyano, nitro, acetyl, propionyl and 1-methoxyiminoethyl, or R¹ and R² together with N-atom to which they are attached, represent pyrrolidin-1-yl, indol-1-yl, indolin-1-yl, 1,2-dihydroquinolin-1-yl, or 1,2,3,4-tetrahydroquinolin-1-yl which may optionally be substituted by methyl.
 4. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1, and a diluent.
 5. A method of combatting unwanted vegetation which comprises applying to such vegetation or to a locus from which it is desired to exclude such vegetation a herbicidally effective amount of a compound according to claim
 1. 6. A compound of the formula ##STR725## wherein X represents C₁₋₃ alkyl, C₂₋₄ alkenyl or halogen, andn' represent 1 to
 5. 